Multi-Functional Nanoscale Platforms: Bridging the Gap between Molecular and Macroscopic Worlds
Lead Research Organisation:
University of Nottingham
Department Name: Sch of Chemistry
Abstract
The control and manipulation of molecules is one of the fundamental challenges of Nanoscience. In this project we intend to build a nanoscale bridge to the molecular world that would enable the study and fabrication of molecules with atomic precision. The aim is to construct addressable, multi-functional nanoscale platforms based on nanotubes (Multi-Functional Nanotubes, MFNT) that are able to control the physiochemical states of molecules and harness their properties for practical applications.
The confinement of molecules inside nanotubes is known to have profound effects on the positions, orientations, and rotational and translation motions of guest-molecules. However, in most cases nanotubes play the role of a passive container influencing molecular behaviour simply due to the restricted space available, thus leading to static molecular architectures. In this project, we will exploit physical (electrical and thermal conductivity, or optical transparency) and chemical (surface charge and functionality) properties of carbon, TiO2 and BN nanotubes to develop MFNT platforms responsive to external stimuli (heat, light, electric potential, or pH). The MFNT system will serve as a conduit for external macroscopic stimuli, channelling them to the level of individual molecules.
Our approach will enable the addressing of optical, electrical and magnetic states of guest-molecules entrapped within MFNT, which will be gauged by spectroscopy and electron microscopy measurement. The control of chemical reactivity of molecules is particularly important as new, previously unknown chemical transformations triggered inside MFNTs may lead to molecular materials with unique structures and properties that are not accessible by any existing approaches.
This ambitious interdisciplinary project, developing at the boundary of physics, chemistry, and materials science, has the potential to change the way we make and study molecules and could provide revolutionary applications for future technologies.
The confinement of molecules inside nanotubes is known to have profound effects on the positions, orientations, and rotational and translation motions of guest-molecules. However, in most cases nanotubes play the role of a passive container influencing molecular behaviour simply due to the restricted space available, thus leading to static molecular architectures. In this project, we will exploit physical (electrical and thermal conductivity, or optical transparency) and chemical (surface charge and functionality) properties of carbon, TiO2 and BN nanotubes to develop MFNT platforms responsive to external stimuli (heat, light, electric potential, or pH). The MFNT system will serve as a conduit for external macroscopic stimuli, channelling them to the level of individual molecules.
Our approach will enable the addressing of optical, electrical and magnetic states of guest-molecules entrapped within MFNT, which will be gauged by spectroscopy and electron microscopy measurement. The control of chemical reactivity of molecules is particularly important as new, previously unknown chemical transformations triggered inside MFNTs may lead to molecular materials with unique structures and properties that are not accessible by any existing approaches.
This ambitious interdisciplinary project, developing at the boundary of physics, chemistry, and materials science, has the potential to change the way we make and study molecules and could provide revolutionary applications for future technologies.
Planned Impact
This project is a relatively short (18 months) and highly-focused research programme that is set to discover radically new ways of making molecules and improving well-known chemical reactions of practical importance. Lying at the core of the project, the concept of nanoscale confinement has the broadest range of implications for the interface between chemistry, physics and material science, fundamentally impacting all these disciplines as well as leading to significant improvements in industrial synthesis which will build on these principles in the long term. Three specific streams of impact are identifies as follows:
Academic community:
Academics researching areas of chemistry related to nanoscience, organic synthesis and catalysis will be the primary beneficiaries from the outputs of this project. The PI has a wide network of academic collaborators who will receive materials prepared in this project for exploring their physiochemical properties by a wide range of experimental techniques.
A highly interdisciplinary nature of this project will stimulate interest from disciplines beyond chemistry. Molecule-nanotube hybrid materials to be constructed and molecular nanoscale transformations to be established in the project will be relevant to nanotechnology, nanomaterials, molecular and surface physics areas of research.
UK Economy:
While the research programme is explicitly aimed at generating fundamental scientific impact, some important discoveries are likely to be exploited in industrial processes. Multi-functional nanoscale platforms will be applied to existing chemical processes of industrial importance, and are expected to enhance the efficiency of existing synthetic schemes through nanoscale confinement. Furthermore, this project aims to demonstrate entirely new types of chemical transformations leading to unique products that cannot be obtained by any other means. If successful, this methodology may change the ways we control chemical reactions and make molecules, thus giving a leading edge to UK chemical and pharmaceutical industries.
Society:
There is a strong interest in nanoscale materials and phenomena in the wider society. Unusual physical and chemical phenomena emerging at nanoscale are stimulating interest in physical sciences among the general public. The results of this project will be widely publicised to inform stakeholders and influence decisions of policymakers as well as general public, using the effective mechanisms established by the PI.
Academic community:
Academics researching areas of chemistry related to nanoscience, organic synthesis and catalysis will be the primary beneficiaries from the outputs of this project. The PI has a wide network of academic collaborators who will receive materials prepared in this project for exploring their physiochemical properties by a wide range of experimental techniques.
A highly interdisciplinary nature of this project will stimulate interest from disciplines beyond chemistry. Molecule-nanotube hybrid materials to be constructed and molecular nanoscale transformations to be established in the project will be relevant to nanotechnology, nanomaterials, molecular and surface physics areas of research.
UK Economy:
While the research programme is explicitly aimed at generating fundamental scientific impact, some important discoveries are likely to be exploited in industrial processes. Multi-functional nanoscale platforms will be applied to existing chemical processes of industrial importance, and are expected to enhance the efficiency of existing synthetic schemes through nanoscale confinement. Furthermore, this project aims to demonstrate entirely new types of chemical transformations leading to unique products that cannot be obtained by any other means. If successful, this methodology may change the ways we control chemical reactions and make molecules, thus giving a leading edge to UK chemical and pharmaceutical industries.
Society:
There is a strong interest in nanoscale materials and phenomena in the wider society. Unusual physical and chemical phenomena emerging at nanoscale are stimulating interest in physical sciences among the general public. The results of this project will be widely publicised to inform stakeholders and influence decisions of policymakers as well as general public, using the effective mechanisms established by the PI.
Publications
Agasti N
(2020)
Cerium Oxide Nanoparticles Inside Carbon Nanoreactors for Selective Allylic Oxidation of Cyclohexene.
in Nano letters
Astle M
(2018)
Synthesis of hydroxylated group IV metal oxides inside hollow graphitised carbon nanofibers: nano-sponges and nanoreactors for enhanced decontamination of organophosphates
in Journal of Materials Chemistry A
Astle M
(2019)
Molybdenum Dioxide in Carbon Nanoreactors as a Catalytic Nanosponge for the Efficient Desulfurization of Liquid Fuels
in Advanced Functional Materials
Aygün M
(2018)
Magnetically Recyclable Catalytic Carbon Nanoreactors
in Advanced Functional Materials
Bhatt A
(2017)
Structure-Activity Relationships of Benzenesulfonamide-Based Inhibitors towards Carbonic Anhydrase Isoform Specificity.
in Chembiochem : a European journal of chemical biology
Botka B
(2014)
Interactions and chemical transformations of coronene inside and outside carbon nanotubes.
in Small (Weinheim an der Bergstrasse, Germany)
Botos A
(2016)
Carbon Nanotubes as Electrically Active Nanoreactors for Multi-Step Inorganic Synthesis: Sequential Transformations of Molecules to Nanoclusters and Nanoclusters to Nanoribbons.
in Journal of the American Chemical Society
Chamberlain T
(2017)
Isotope Substitution Extends the Lifetime of Organic Molecules in Transmission Electron Microscopy
in Small
Chamberlain TW
(2017)
Stop-Frame Filming and Discovery of Reactions at the Single-Molecule Level by Transmission Electron Microscopy.
in ACS nano
Chamberlain TW
(2015)
Isotope substitution extends the lifetime of organic molecules in transmission electron microscopy.
in Small (Weinheim an der Bergstrasse, Germany)
Chamberlain TW
(2015)
Switching intermolecular interactions by confinement in carbon nanotubes.
in Chemical communications (Cambridge, England)
Chamberlain TW
(2014)
Catalytic nanoreactors in continuous flow: hydrogenation inside single-walled carbon nanotubes using supercritical CO2.
in Chemical communications (Cambridge, England)
Cornelio B
(2015)
Palladium nanoparticles in catalytic carbon nanoreactors: the effect of confinement on Suzuki-Miyaura reactions
in Journal of Materials Chemistry A
Del Carmen Gimenez-Lopez M
(2016)
Extremely Stable Platinum-Amorphous Carbon Electrocatalyst within Hollow Graphitized Carbon Nanofibers for the Oxygen Reduction Reaction.
in Advanced materials (Deerfield Beach, Fla.)
Jordan JW
(2019)
Host-Guest Hybrid Redox Materials Self-Assembled from Polyoxometalates and Single-Walled Carbon Nanotubes.
in Advanced materials (Deerfield Beach, Fla.)
Lebedeva MA
(2016)
Stabilising the lowest energy charge-separated state in a {metal chromophore - fullerene} assembly: a tuneable panchromatic absorbing donor-acceptor triad.
in Chemical science
Lebedeva MA
(2015)
Harnessing the Synergistic and Complementary Properties of Fullerene and Transition-Metal Compounds for Nanomaterial Applications.
in Chemical reviews
Maggini L
(2014)
Fullerene-driven encapsulation of a luminescent Eu(III) complex in carbon nanotubes.
in Nanoscale
Markevich A
(2016)
Electron beam controlled covalent attachment of small organic molecules to graphene.
in Nanoscale
McSweeney RL
(2016)
Direct Measurement of Electron Transfer in Nanoscale Host-Guest Systems: Metallocenes in Carbon Nanotubes.
in Chemistry (Weinheim an der Bergstrasse, Germany)
McSweeney RL
(2014)
Single-walled carbon nanotubes as nano-electrode and nano-reactor to control the pathways of a redox reaction.
in Chemical communications (Cambridge, England)
Miners S
(2019)
Steric and Electronic Control of 1,3-Dipolar Cycloaddition Reactions in Carbon Nanotube Nanoreactors
in The Journal of Physical Chemistry C
Miners SA
(2016)
Chemical reactions confined within carbon nanotubes.
in Chemical Society reviews
Pineux F
(2015)
Biotechnological promises of Fe-filled CNTs for cell shepherding and magnetic fluid hyperthermia applications.
in Nanoscale
Pollack A
(2014)
Electronic property modification of single-walled carbon nanotubes by encapsulation of sulfur-terminated graphene nanoribbons.
in Small (Weinheim an der Bergstrasse, Germany)
Sinitsa AS
(2017)
Formation of Nickel Clusters Wrapped in Carbon Cages: Toward New Endohedral Metallofullerene Synthesis.
in Nano letters
Skowron ST
(2017)
Chemical Reactions of Molecules Promoted and Simultaneously Imaged by the Electron Beam in Transmission Electron Microscopy.
in Accounts of chemical research
Solomonsz WA
(2014)
Evaluating the effects of carbon nanoreactor diameter and internal structure on the pathways of the catalytic hydrosilylation reaction.
in Small (Weinheim an der Bergstrasse, Germany)
Zoberbier T
(2016)
Investigation of the Interactions and Bonding between Carbon and Group VIII Metals at the Atomic Scale.
in Small (Weinheim an der Bergstrasse, Germany)
| Description | Carbon nanotubes have been demonstrated as highly effective nano-reactors in over 15 different types of reactions: 1) confinement of reacting molecules at nanoscale allowed control of the reaction selectivity; 2) catalytic reactions carried out in nanotubes enabled improvements in selectivity and, most importantly, durability and effective re-usability of catalyst, including precious metals (Pt, Pd, Ru); 3) carbon nanotubes have been integrated in electrochemical devices that enable addressing of redox-active confined molecules, leading to improved electrical communication between the molecules and the electrode, and drastically enhancing durability of electrocatalytic nanoparticles (e.g. Pt) confined in nanotubes, outperforming state of the art materials for key technological applications, such as fuel cells. Overall, this project demonstrated nanotubes as a physical bridge between the macro-world and the world of molecules, opening the door for new ways of making and studying molecules. |
| Exploitation Route | Our approach and materials developed in this project can be utilized for improving sustainability of the use of precious metals (such as platinum, palladium etc), and applied for sequestration, and decontamination of hazardous materials. Continuous flow catalytic nanoreactors will be scaled up for industrial synthesis. New methodologies for recycling and reusing precious metal catalysts. New generation of fuel cells with a much longer useful lifetime. Energy storage materials. |
| Sectors | Chemicals,Energy,Environment |
| URL | https://www.nottingham.ac.uk/nanocarbon/ |
| Description | Horizon 2020 |
| Amount | € 2,962,000 (EUR) |
| Organisation | European Commission |
| Sector | Public |
| Country | European Union (EU) |
| Start | 01/2016 |
| End | 12/2018 |
| Description | Jeremy Sloan, Warwick University |
| Organisation | University of Warwick |
| Country | United Kingdom |
| Sector | Academic/University |
| PI Contribution | Synthesis of carbon nanomaterials |
| Collaborator Contribution | Advanced TEM image simulation and analysis |
| Impact | Joint publication in Journal of American Chemical Society in 2016 |
| Start Year | 2015 |
| Description | Kazu Suenaga, Tsukuba, Japan |
| Organisation | National Institute of Advanced Industrial Science and Technology |
| Country | Japan |
| Sector | Public |
| PI Contribution | Synthesis and advanced characterization of carbon nanomaterials |
| Collaborator Contribution | Advanced TEM and STEM low-voltage analysis |
| Impact | Joint publication in Journal American Chemical Society in 2016 |
| Start Year | 2015 |
| Description | University of Ulm - Prof. Ute Kaiser |
| Organisation | University of Ulm |
| Country | Germany |
| Sector | Academic/University |
| PI Contribution | I provide nanomaterials for advanced electron microscopy experiments in Ulm. |
| Collaborator Contribution | Collaborators in Ulm University (Germany) enable access to cutting-edge electron microscopy facilities essential for my work. |
| Impact | Several high-profile publications (including 3 Nature group articles), co-supervision of PhD students. |
| Start Year | 2007 |